This appl""n is a 371 of PCT/EP00/08659 filed Sep. 5, 2000.
A The present invention relates to new selectively herbicidal compositions for controlling grasses and weeds in crops of useful plants, especially in crops of maize and cereals, which compositions comprise a 3-hydroxy-4-(4-methylphenyl)-5-oxo-pyrazoline herbicide, a safener (counter-agent, antidote) and an oil additive and protect the useful plants but not the weeds against the phytotoxic action of the herbicide, and to the use of such compositions in controlling weeds in crops of useful plants.
When using herbicides, the cultivated plants may also suffer considerable damage, depending on, for example, the amount of herbicide used and the method of application, the cultivated plant, the nature of the soil and climatic conditions, for example hours of daylight, temperature and amounts of rainfall. In order to deal with that and similar problems, various substances have already been proposed as safeners, which are capable of antagonising the harmful effect of the herbicide on the cultivated plant, that is to say are capable of protecting the cultivated plant, without appreciably impairing the herbicidal action on the weeds to be acontrolled.
It has been found that the proposed safeners often act very specifically both with respect to the cultivated plants and with respect to the herbicide, and in some cases also in dependence on the method of application, that is to say, a particular safener is often suitable only for a particular cultivated plant and a specific class of herbicidal substance or a particular herbicide. For example, it has been found that although the safeners cloquintocet and cloquintocet-mexyl and mefenpyr and mefenpyr-diethyl, known from EP-A-0 191 736 (compound 1.316) and WO 91/07874 (Example 3) and from The Pesticide Manual, 11th Ed., British Crop Protection Council, Entry No. 154 and 462, are capable of protecting the cultivated plant from the phytotoxic action of particular 3-hydroxy-4-(4-methylphenyl)-5-oxo-pyrazoline derivatives, they do, however, reduce the herbicidal action on weeds in some cases.
U.S. Pat. No. 4,834,908 discloses that certain oil additive combinations can increase the herbicidal activity of compounds from the class of the cyclohexanediones, benzothiadiazinone dioxides, diphenyl ether herbicides and aryloxyphenoxy herbicides.
Although the 3-hydroxy-4-(4-methylphenyl)-5-oxo-pyrazoline derivatives are structurally completely different from the compounds disclosed in U.S. Pat. No. 4,834,908, the combination of such oil additives with the said 3-hydroxy-4-(4-methylphenyl)-5-oxo-pyrazoline derivatives likewise results in an increase in herbicidal activity but the cultivated plant is also damaged to a considerable extent. That herbicide/oil additive mixture is therefore not suitable for selectively controlling weeds in crops of useful plants.
It has now been found, surprisingly, that weeds can be selectively controlled very successfully using the particular 3-hydroxy-4-(4-methylphenyl)-5-oxo-pyrazoline herbicides without damaging the cultivated plant, by applying those compounds in combination with an additive comprising an oil of vegetable or animal origin or a mineral oil, alkyl esters thereof, or mixtures of those oils and oil derivatives, and with the safeners cloquintocet or mefenpyr.
The present invention accordingly relates to a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of
a) a herbicidally effective amount of a compound of formula I 
xe2x80x83wherein
R1 and R3 are, each independently of the other, halogen, nitro, cyano, C1-C4alkyl, C2-C4-alkenyl, C2-C4alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C2-C6alkoxyalkyl, C2-C6alkylthioalkyl, hydroxy, mercapto, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, carbonyl, carboxyl, C1-C4alkylcarbonyl, C1-C4hydroxyalkyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino or di(C1-C4alkyl)amino;
R4 and R5 together are a group
xe2x80x94Cxe2x80x94R6(R7)xe2x80x94Oxe2x80x94Cxe2x80x94R8(R9)xe2x80x94Cxe2x80x94R10(R11)xe2x80x94Cxe2x80x94R12(R13)xe2x80x94 (Z1),
xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94 (Z2), or
xe2x80x94Cxe2x80x94R22(R23)xe2x80x94Cxe2x80x94R24(R25)xe2x80x94Cxe2x80x94R26(R27)xe2x80x94Oxe2x80x94Cxe2x80x94R28(R29)xe2x80x94 (Z3),
wherein R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28 and R29 are, each independently of the others, hydrogen, halogen, C1-C4alkyl or C1-C4haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the groups
Z1, Z2 or Z3 or that alkylene ring bridges at least one ring atom of the groups Z1, Z2 or Z3;
G is hydrogen, xe2x80x94C(X1)xe2x80x94R30, xe2x80x94C(X2)xe2x80x94X3xe2x80x94R31, xe2x80x94C(X4)xe2x80x94N(R32)xe2x80x94R33, xe2x80x94SO2xe2x80x94R34, an alkali metal, alkaline earth metal, sulfonium or ammonium cation, or xe2x80x94P(X5)(R35)xe2x80x94R36 or xe2x80x94CH2xe2x80x94X6xe2x80x94R37;
X1, X2, X3, X4, X5 and X6 are, each independently of the others, oxygen or sulfur;
R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C10alkyl, C1-C10-haloalkyl, C1-C10cyanoalkyl, C1-C10nitroalkyl, C1-C10aminoalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C10alkoxy-alkyl, C4-C10-alkenyloxy-alkyl, C4-C10alkynyloxy-alkyl, C2-C10alkylthio-alkyl, C1-C5alkysulfoxyl-C1-C5alkyl, C1-C5alkylsulfonyl-C1-C5alkyl, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C5alkylcarbonyl-C1-C5alkyl, C1-C5alkoxycarbonyl-C1-C5alkyl, C1-C5amino-carbonyl-C1-C5alkyl, C2-C8dialkyl-amino-carbonyl-C1-C5alkyl, C1-C5alkylcarbonylamino-C1-C5alkyl, C2-C5alkylcarbonyl-(C1-C5alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, phenyl-C1-C5alkyl, heteroaryl-C1-C5alkyl, phenoxy-C1-C5alkyl, heteroaryloxy-C1-C5alkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diphenylamino, C3-C7cycloalkylamino, C1-C3alkyl-, C1-C3-haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkylamino, di-C3-C7cycloalkylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7cycloalkylamino, C3-C7cycloalkoxy or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkoxy;
R34, R35 and R36 are hydrogen, C1-C10alkyl, C1-C10haloalkyl, C1-C10cyanoalkyl, C1-C10-nitroalkyl, C1-C10aminoalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C10alkoxy-alkyl, C4-C10alkenyloxy-alkyl, C4-C10alkynyloxy-alkyl, C2-C10alkylthio-alkyl, C1-C5alkysulfoxyl-C1-C5alkyl, C1-C5alkylsulfonyl-C1-C5alkyl, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C5alkylcarbonyl-C1-C5alkyl, C1-C5alkoxycarbonyl-C1-C5alkyl, C1-C5amino-carbonyl-C1-C5alkyl, C2-C8dialkylamino-carbonyl-C1-C5alkyl, C1-C5alkylcarbonylamino-C1-C5alkyl, C2-C5alkylcarbonyl-(C1-C5alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, phenyl-C1-C5alkyl, heteroaryl-C1-C5alkyl, phenoxy-C1-C5alkyl, heteroaryloxy-C1-C5alkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl or heteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroaryl-amino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diphenylamino, C3-C7cycloalkylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkylamino, di-C3-C7Cycloalkylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7cycloalkylamino, C3-C7cycloalkoxy, C1-C3alkyl-, C1-C3haloalkyl-, C1-C-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkoxy, C1-C10alkoxy, C1-C10haloalkoxy, C1-C5alkylamino, C2-C8dialkylamino and benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, formyl, acetyl, propionyl, carboxyl, C1-C5alkoxycarbonyl, methylthio, ethylthio or by nitro; and
R37 is C1-C10alkyl, C1-C10haloalkyl, C1-C10cyanoalkyl, C1-C10nitroalkyl, C1-C10aminoalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C10alkoxy-alkyl, C4-C10alkenyloxy-alkyl, C4-C10alkynyloxy-alkyl, C2-C10alkylthio-alkyl, C1-C5alkysulfoxyl-C1-C5alkyl, C1-C5alkylsulfonyl-C1-C5alkyl, C2-C8alkylideneamino-oxy-C1-C5alkyl, C1-C5alkylcarbonyl-C1-C5alkyl, C1-C5alkoxycarbonyl-C1-C5alkyl, C1-C5aminocarbonyl-C1-C5alkyl, C2-C8dialkylamino-carbonyl-C1-C5alkyl, C1-C5alkylcarbonylamino-C1-C5alkyl, C2-C5alkylcarbonyl-(C1-C5alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, henyl-C1-C5alkyl, heteroaryl-C1-C5alkyl, phenoxy-C1-C5alkyl, heteroaryloxy-C1-C5alkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, phenyl, or C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenyl or heteroaryl, or heteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted heteroarylamino, diheteroarylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diheteroarylamino, phenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted phenylamino, diphenylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted diphenylamino, C3-C7cycloalkylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkylamino, di-C3-C7cycloalkylamino, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted di-C3-C7Cycloalkylamino, C3-C7cycloalkoxy, C1-C3alkyl-, C1-C3haloalkyl-, C1-C3alkoxy-, C1-C3haloalkoxy-, halo-, cyano- or nitro-substituted C3-C7cycloalkoxy or C1-C10alkylcarbonyl; and salts and diastereoisomers of the compounds of formula I, with the proviso that R1 and R3 are not simultaneously methyl;
b) an amount, which is effective for antagonism of the herbicide, of a safener selected from cloquintocet, an alkali metal, alkaline earth metal, sulfonium or ammonium cation of cloquintocet, or cloquintocet-mexyl, mefenpyr, an alkali metal, alkaline earth metal, sulfonium or ammonium cation of mefenpyr, and mefenpyr-diethyl; and
c) an additive comprising an oil of vegetable or animal origin, or a mineral oil, alkyl esters thereof or mixtures of those oils and oil derivatives.
In the above definitions, halogen is to be understood as fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. The alkyl groups occurring in the substituent definitions are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, and the pentyl and hexyl isomers. Suitable cycloalkyl substituents contain from 3 to 6 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. They may be substituted one or more times by halogen, preferably fluorine, chlorine or bromine. Alkenyl is to be understood as, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl. Haloalkyl groups preferably have a chain length of from 1 to 4 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl, preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. Suitable haloalkenyl radicals include alkenyl groups substituted one or more times by halogen, halogen being fluorine, chlorine, bromine or iodine and especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the C2-C6alkenyl groups substituted once, twice or three times by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or a pentyloxy or hexyloxy isomer, preferably methoxy or ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkoxyalkyl groups preferably have from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. Phenyl may be in substituted form, in which case the substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions to the ring attachment point. Heteroaryl groups are usually aromatic heterocycles that contain preferably from 1 to 3 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of suitable heterocycles and heteroaromatic compounds are: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetane, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzothiazole, quinoxaline and quinoline. Those heterocycles and heteroaromatic compounds may be further substituted, for example by halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, thioalkyl, alkylamino or by phenyl. The C2-C10-alkenyl- and -alkynyl groups R34 may be mono- or poly-unsaturated. They contain preferably from 2 to 12 carbon atoms, especially from 2 to 6 carbon atoms.
Alkali metal, alkaline earth metal or ammonium cations for the substituent G are, for example, the cations of sodium, potassium, magnesium, calcium and ammonium. Preferred sulfonium cations are especially trialkylsulfonium cations wherein the alkyl radicals each contain preferably from 1 to 4 carbon atoms.
The left-hand free valence of the groups Z1, Z2 and Z3 is bound to the 1-position and the right-hand free valence to the 2-position of the pyrazoline ring.
Compounds of formula I wherein it is possible for an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains from 2 to 6 carbon atoms, to be fused or spiro-bound to the groups Z1, Z2 and Z3 have, for example, the following structure: 
Compounds of formula I wherein in the groups Z1, Z2 or Z3 an alkylene ring bridges at least one ring atom of the groups Z1, Z2 or Z3, have, for example, the following structure: 
In herbicides of formula I that are preferred for the compositions in accordance with the invention, R1 and R3 are each independently of the other ethyl, haloethyl, ethynyl, C1-C2alkoxy or C1-C2haloalkoxy.
Preference is also given to those compositions in accordance with the invention wherein R4 and R5 together are a Z2 group xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94 (Z2) wherein R14, R15, R16, R17, R18, R19, R20 and R21 are very especially hydrogen.
In a further preferred group of compositions according to the invention, in formula I R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkil-C1-C5alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkysulfinyl-C1-C2alkyl, C1-C2alkylsulfonyl-C1-C2alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1-C5alkoxycarbonyl-C1-C2alkyl, C1-C5aminocarbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C5alkylcarbonylamino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl;
R34, R35 and R36, are each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkysulfinyl-C1-C2alkyl, C1-C2alkylsulfonyl-C1-C2alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1-C5alkoxycarbonyl-C1-C2alkyl, C1-C5aminocarbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C5alkylcarbonylamino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C1-C5alkoxycarbonyl or by C1- or C2-haloalkyl; and
R37 is C1-C8alkyl, C1-C8haloalkyl, C1-C8cyanoalkyl, C1-C8nitroalkyl, C1-C8aminoalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C1-C5alkylamino-C1-C5alkyl, C2-C8dialkylamino-C1-C5alkyl, C3-C7cycloalkyl-C1-C5alkyl, C2-C4alkoxy-alkyl, C4-C6alkenyloxy-alkyl, C4-C6alkynyloxy-alkyl, C2-C4alkylthio-alkyl, C1-C4alkylsulfinyl-C1-C2alkyl, C1-C2alkylsulfonyl-C1-C2alkyl, C2-C4alkylideneamino-oxy-C1-C2alkyl, C1-C5alkylcarbonyl-C1-C2alkyl, C1-C5alkoxycarbonyl-C1-C2alkyl, C1-C5amino-carbonyl-C1-C2alkyl, C2-C8dialkylamino-carbonyl-C1-C2alkyl, C1-C5alkylcarbonylamino-C1-C2alkyl, C2-C5alkylcarbonyl-(C1-C2alkyl)-aminoalkyl, C3-C6trialkylsilyl-C1-C5alkyl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, phenyl or heteroaryl, benzyloxy or phenoxy, it being possible for the benzyl and phenyl groups themselves to be substituted by halogen, nitro, cyano, amino, dimethylamino, hydroxy, methoxy, ethoxy, methylthio, ethylthio, formyl, acetyl, propionyl, carboxyl, C1-C2alkoxycarbonyl or by C1- or C2-haloalkyl; or R37 is C1-C8alkylcarbonyl.
Special preference is given to those compositions according to the invention wherein, in formula I, R30, R31, R32 and R33 are, each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C3-C7cycloalkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl;
R34, R35 and R36 are, each independently of the others, hydrogen, C1-C8alkyl, C1-C8haloalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C3-C7cycloalkyl-C1-C2alkyl, C2-C4alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, C1-C6alkoxy, C1-C3alkylamino or di(C1-C3alkyl)amino; and
R37 is C1-C8alkyl, C1-C8haloalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C3-C8cycloalkyl, C3-C7cycloalkyl-C1-C2alkyl, C2-C4alkoxy-alkyl, phenyl, heteroaryl, phenyl-C1-C2alkyl, heteroaryl-C1-C2alkyl, phenoxy-C1-C2alkyl, heteroaryloxy-C1-C2alkyl, C1-C6alkoxy, C1-C3alkylamino, di-(C1-C3alkyl)-amino or C1-C8alkylcarbonyl.
An especially preferred safener in the composition according to the invention is cloquintocet-mexyl. As a suitable oil additive, special emphasis should be given within the context of the invention to MERGE(copyright) and Actiprom(copyright).
The compositions according to the invention may also comprise salts that the compounds of formula I may form with acids. Suitable acids for the formation of acid addition salts are both organic and inorganic acids. Examples of such acids are hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid. The salts of the compounds of formula I having acid hydrogen also are alkali metal salts, for example sodium and potassium salts; alkaline earth metal salts, for example calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, or are salts with other organic nitrogen bases. Suitable salt formers are accordingly alkali metal and alkaline earth metal hydroxides, especially the hydroxides of lithium, sodium, potassium, magnesium or calcium, with those of sodium or potassium being given special importance.
Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl-ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, N-methylmorpholine, thio-morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary aryl amines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylene-diamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
If non-chiral starting materials are employed, the asymmetrically substituted compounds of formula I obtained in the processes described in this Application are generally in the form of racemates. The stereoisomers can then be separated on the basis of their physicochemical properties according to known methods, such as, for example, fractional crystallisation following salt formation with optically pure bases, acids or metal complexes, or by chromatographic procedures, such as, for example, high-pressure liquid chromatography (HPLC) on acetyl cellulose. In the present invention, xe2x80x9ccompounds of formula Ixe2x80x9d are to be understood as including both the concentrated and optically pure forms of the stereoisomers in question and the racemates and diastereoisomers. Where no special mention is made of individual optical antipodes, the formula in question is to be understood as referring to the racemic mixtures that are obtained in the preparation process mentioned. When an aliphatic Cxe2x95x90C double bond is present, geometric isomerism may also occur.
The compounds of formula I may, also in dependence upon the nature of the substituents, occur as geometric and/or optical isomers and isomeric mixtures and as tautomers and tautomeric mixtures. For example, the compounds of formula I wherein the group G is hydrogen can occur in the following tautomeric equilibria: 
When G is other than hydrogen and Z is the group Z1 or Z3, or when G is other than hydrogen and Z2 is asymmetrically substituted, fused or spiro-bounded, the compound of formula I may occur as an isomer of formula Id 
Processes for the preparation of compounds that differ from the compounds of formula I according to the present invention in respect of the meanings of the substituents R4 and R5 are described, for example, in WO 96/21652. The compounds of formula I according to the present invention can be prepared analogously to the processes described in WO 96/21652.
The compounds of formula II 
wherein R1, R3, R4 and R5 are as defined for formula I, used as starting materials for such processes can be prepared, for example, by reacting a compound of formula III 
wherein R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl and R1 and R3 are as defined for formula I, in an inert organic solvent, optionally in the presence of a base, with a compound of formula IV or IVa 
wherein R4 and R5 are as defined for formula I. Further preparation processes leading to compounds of formula II are also described, for example, in WO 92/16510.
The compounds of formula III either are known or can be prepared analogously to known processes. Processes for the preparation of compounds of formula III and the reaction thereof with hydrazines are described, for example, in WO 97/02243. Compounds of formula III wherein R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl and R1, R2 and R3 are as defined for formula I can be prepared analogously to methods known to the person skilled in the art. For example, compounds of formula III wherein R is C1-C6alkyl or C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl and R1, R2 and R3 are each independently of the others, C1-C4alkyl, C2-C4alkenyl or C2-C4alkynyl can be prepared according to the process of cross-coupling according to Stille (J. K. Stille, Angew. Chem. 1986, 98, 504-519), Sonogashira (K. Sonogashira et al., Tetrahedron Lett. 1975, 4467-4470), Suzuki (N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483) or Heck (R. F. Heck, Org. React. 1982, 27, 345-390) and, optionally, subsequent hydrogenation. The following Reaction Scheme illustrates this procedure: 
The compounds of formulae IV and IVa either are known or can be prepared analogously to known processes. Processes for the preparation of compounds of formula IV are described, for example, in WO 95/00521. Those compounds can be prepared, for example, by heating a compound of formula V 
wherein R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy or benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5 are as defined for formula I, in an inert solvent in the presence of a base or acid. Compounds of formula V wherein R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy or benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5 are as defined for formula I can be prepared, for example by reacting a compound of formula VI 
wherein R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy or benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy, in the presence of a base and an inert solvent, with a compound of formula VII
y"Brketopenst"Z1, Z2, or Z3"Brketclosest",xe2x80x83xe2x80x83(VII)
wherein Y is halogen, alkyl/aryl sulfonate xe2x80x94OSO2R43, preferably bromine, chlorine, iodine, mesylate (R43=CH3), triflate (R43=CF3) or tosylate (R43=p-tolyl) and Z1, Z2, and Z3 are as defined for formula I. In formula VII, the free valences of the groups Z1, Z2, and Z3 are in each case bound to the group Y. Compounds of formula VI and VII are known or can be prepared analogously to methods known to the person skilled in the art.
Compounds of formula IV wherein R4 and R5 together are a group Z2 xe2x80x94Cxe2x80x94R14(R15)xe2x80x94Cxe2x80x94R16(R17)xe2x80x94Oxe2x80x94Cxe2x80x94R18(R19)xe2x80x94Cxe2x80x94R20(R21)xe2x80x94 (Z2) wherein R14, R15, R16, R17, R18, R19, R20 and R21 are hydrogen can be prepared, for example, in accordance with the following Reaction Scheme: 
The end products of formula I can be isolated in conventional manner by concentrating and/or evaporating off the solvent and by recrystallising or triturating the solid residue in solvents in which they are not readily soluble, such as ethers, alkanes, aromatic hydrocarbons or chlorinated hydrocarbons, or they can be purified by means of chromatography. Salts of compounds of formula I can be prepared in a manner known per se. Such preparation methods are described, for example, in WO 96/21652.